Dye mixtures, 1:2 cobalt complex formazan dyes and their use

ABSTRACT

Dye mixtures which comprise at least one 1:2 cobalt complex dye of the formazan compound of the formula                    
     in which 
     X is substituted or unsubstituted C 1 -C 8 alkyl, phenyl, naphthyl, furyl or thienyl, 
     R 1  and R 2  independently of one another are hydrogen or substituted or unsubstituted C 1 -C 8 alkyl, phenyl or naphthyl, 
     m is a number from 1 to 4 and 
     the rings I, II, III and IV may be further substituted, 
     together with at least one anthraquinone dye of the formula (2) as defined in claim 1, 
     or together with at least one 1:2 chromium or 1:2 cobalt complex dye of two identical or different azo compounds from the group comprising the compounds of the formulae (3), (4), (5) and (6) as defined in claim 1; 
     and novel 1:2 cobalt complex formazan dyes. 
     The dye mixtures are particularly suitable for dyeing or printing natural and synthetic polyamide fiber materials, dyeings or prints having good fastnesses being obtained.

This application is a continuation of application Ser. No. 08/242,515,filed May 13, 1994, abandoned.

The present invention relates to mixtures of 1:2 cobalt complex formazandyes with anthraquinone dyes or 1:2 chromium or 1:2 cobalt complex azodyes, which are particularly suitable for dyeing or printing natural orsynthetic textile polyamide fibre materials and in particular have verygood fastness properties. The present invention furthermore relates tothe novel 1:2 cobalt complex formazan dyes.

The present invention relates to dye mixtures which comprise at leastone 1:2 cobalt complex dye of the formazan compound of the formula

in which

X is substituted or unsubstituted C₁-C₈alkyl, phenyl, naphthyl, furyl orthienyl,

R₁ and R₂ independently of one another are hydrogen or substituted orunsubstituted C₁-C₈alkyl, phenyl or naphthyl,

m is a number from 1 to 4 and

the rings I, II, III and IV may be further substituted,

together with at least one anthraquinone dye of the formula (2)

in which

Y is hydrogen or substituted or unsubstituted C₁-C₈alkyl, cyclohexyl,phenyl or 1,2,3,4-tetrahydronaphthyl and

Z is substituted or unsubstituted C₁-C₈alkyl, cyclohexyl, phenyl or1,2,3,4-tetrahydronaphthyl,

and in which the ring V of the anthraquinone dye of the formula (2) maybe further substituted by one or two hydroxyl groups,

or together with at least one 1:2 chromium or 1:2 cobalt complex dye oftwo identical or different azo compounds from the group comprisingcompounds of the formulae (3), (4), (5) and (6)

in which R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ andR₁₆ independently of one another are hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, halogen, sulfo, hydroxyl, nitro, sulfamoyl orN—C₁-C₄alkylsulfamoyl, which is unsubstituted or further substituted inthe alkyl moiety part by hydroxyl or C₁-C₄alkoxy.

The 1:2 cobalt complex formazan dyes of the formula (1) are preferablysymmetric cobalt complex dyes.

Substituents of a phenyl, naphthyl, furyl or thienyl radical X and ofrings I, II, III and IV of the formazan compound of the formula (1) are,in addition to the radical of the formula —SO₂N(R₁)R₂, independently ofone another, for example, C₁-C₄alkyl, for example methyl or ethyl;C₁-C₄alkoxy, for example methoxy or ethoxy; unsubstituted orhalogen-substituted C₂-C₄alkanoylamino, for example acetylamino,propionylamino or α,β-dibromopropionylamino; hydroxyl; sulfo; nitro;carboxyl; cyano; amino; halogen, for example fluorine, chlorine orbromine; C₁-C₄alkylsulfonyl which is unsubstituted or substituted in thealkyl moiety by hydroxyl or C₁-C₄alkoxy; vinylsulfonyl;α-halogenoacryloylamino; radicals of the formulae —OR, —NHCOR′, —COOR″,CONHR′″ and SO₂R″″, in which R, R′, R″, R′″ and R″″ independently of oneanother are phenyl or naphthyl and R′ can additionally be C₁-C₄alkyl; ortriazinylamino, which can be further substituted by halogen,C₁-C₄alkylamino, phenylamino or N—C₁-C₄alkyl-N-phenylamino. The phenylor naphthyl radicals mentioned can be substituted as defined above for Xand the rings I, II, III and IV, in particular by C₁-C₄alkyl,C₁-C₄alkoxy, C₂-C₄alkanoylamino, hydroxyl, sulfo, nitro, carboxyl,cyano, halogen or C₁-C₄alkylsulfonyl which is unsubstituted or furthersubstituted in the alkyl moiety by hydroxyl or C₁-C₄alkoxy.

In addition to the radical of the formula —SO₂N(R₁)R₂, preferredsubstituents for X and the rings I, II, III and IV of the formazancompound of the formula (1) are C₁-C₄alkyl, C₁-C₄alkoxy,C2-C₄alkanoylamino, C₁-C₄alkylsulfonyl, C₁-C₄hydroxyalkylsulfonyl,halogen, sulfo, hydroxyl, carboxyl and nitro.

X is preferably phenyl, which can be substituted, for example, asdefined above.

Phenyl or naphthyl radicals R₁ and R₂ can be unsubstituted orsubstituted. Examples of such substituents are C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl, halogen, sulfo, hydroxyl,carboxyl, nitro, sulfamoyl and N—C₁-C₄alkylsulfamoyl which isunsubstituted or further substituted in the alkyl moiety by hydroxyl orC₁-C₄alkoxy.

C₁-C₈alkyl radicals X, R₁ and R₂ independently of one another are, forexample, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, pentyl, hexyl, heptyl or octyl, and the correspondingradicals which are substituted, for example, by hydroxyl, C₁-C₄alkoxy orhalogen. C₁-C₄alkyl, which can be substituted as defined, is preferredhere.

R₁ and R₂ are preferably independently of one another hydrogen,C₁-C₈alkyl or phenyl, where the alkyl and phenyl radicals can besubstituted as defined above.

R₁ and R₂ are preferably independently of one another hydrogen,C₁-C₄alkyl which is unsubstituted or substituted by hydroxyl orC₁-C₄alkoxy, or phenyl which is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl,C₁-C₄hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl, nitro,sulfamoyl or N—C₁-C₄alkylsulfamoyl which is unsubstituted or furthersubstituted in the alkyl moiety by hydroxyl or C₁-C₄alkoxy. Inparticular, one of the radicals R₁ and R₂ is hydrogen here.

R₁ and R₂ are particularly preferably hydrogen, C₁-C₄alkyl which isunsubstituted or substituted by hydroxyl, or phenyl which isunsubstituted or substituted by sulfo, carboxyl or sulfamoyl. Inparticular, one of the radicals R₁ and R₂ is hydrogen here. R₁ and R₂are especially preferably independently of one another hydrogen orC₁-C₄alkyl, in particular hydrogen or methyl.

m is preferably the number 1 or 2, in particular the number 2.

Substituents of phenyl radicals Y and Z are, for example:

C₁-C₁₂alkyl; C₁-C₄alkoxy; C₂-C₄alkanoylamino; hydroxyl; sulfo; nitro;carboxyl; cyano; amino; halogen; benzoylaminomethyl; chloroacetylamino;chloroacetylaminomethyl; α-chloroacryloylaminomethyl;acryloylaminomethyl; or phenoxy, phenylcarbonylamino, phenylsulfonyloxy,phenylsulfonylamino, phenylsulfonylaminomethyl orN-methyl-phenylsulfonylaminomethyl, where the phenyl radicals can befurther substituted as defined above for Y and Z. The radical Zfurthermore can be an anthraquinone dye radical bonded via a bridgemember; examples of these are the anthraquinone dyes of the followingformula (11).

C₁-C₈alkyl radicals Y and Z independently of one another are, forexample, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, pentyl, hexyl, heptyl or octyl, where the alkyl radicals canbe substituted by phenyl and the phenyl radical can be furthersubstituted as defined above for phenyl radicals Y and Z. Preferredsubstituents of the phenyl radical here are C₁-C₁₂alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, hydroxyl, sulfo, nitro, carboxyl, cyano, amino,halogen, benzoylaminomethyl, chloroacetylamino, chloroacetylaminomethyl,a-chloroacryloylaminomethyl or acryloylaminomethyl.

Cyclohexyl radicals Y and Z independently of one another are, inaddition to unsubstituted cyclohexyl, cyclohexyl substituted, forexample, by C₁-C₄alkyl, phenylsulfonylamino or benzyl, where the phenylradicals can be further substituted, for example, by C₁-C₄alkyl,C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo or halogen.

1,2,3,4-Tetrahydronaphthyl radicals Y and Z independently of one anotherare, in addition to unsubstituted 1,2,3,4-tetrahydronaphthyl, theradical substituted, for example, by sulfo.

If the anthraquinone dye of the formula (2) contains one or two hydroxylgroups in ring V, these are as a rule bonded in the 1- and/or2-position.

The total number of sulfo groups in the anthraquinone dye of the formula(2) is one or two.

C₁-C₄alkyl radicals R₃ to R₁₆ independently of one another are methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, inparticular methyl.

C₁-C₄alkoxy radicals R₃ to R₁₆ independently of one another are methoxy,ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy ortert-butoxy, in particular methoxy.

C₂-C₄Alkanoylamino radicals R₃ to R₁₆ independently of one another are,for example, acetylamino or propionylamino, in particular acetylamino.Halogen atoms R₃ to R₁₆ independently of one another are, for example,fluorine, chlorine or bromine, in particular chlorine.

The formazan compounds of the formula (1) are preferably compounds ofthe formula

in which R₁, R₂ and m are as defined and preferred above; and the phenylradicals can contain no further substituents or are further substitutedas defined above for rings I, II, III and IV. Preferably, the phenylradicals of the compound of the formula (7) may be further substitutedby C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, C₁-C₄alkylsulfonyl,C₁-C₄hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl or nitro.

The formazan compounds of the formula (1) are particularly preferablycompounds of the formula

in which R₁ and R₁′ independently of one another are hydrogen orC₁-C₄alkyl and the phenyl radicals contain no further substituents orcan be further substituted as defined above for rings I, II, III and IV.Preferably, the phenyl radicals of the compound of the formula (8) maybe further substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino,C₁-C₄alkylsulfonyl, C₁-C₄hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl,carboxyl or nitro. The phenyl radicals of the compound of the formula(8) preferably contain no further substituents.

The formazan compounds of the formula (1) are especially preferablycompounds of the formula

in which the phenyl radicals contain no further substituents or can befurther substituted as defined above for the compound of the formula(8). Preferably, the phenyl radicals of the compound of the formula (8a)contain no further substituents.

Preferred anthraquinone dyes of the formula (2) are anthraquinone dyesof the formula

in which Z₁ is phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen,benzoylaminomethyl, chloroacetylamino, chloroacetylaminomethyl orα-chloroacryloylaminomethyl; phenyl-C₁-C₈alkyl, where the phenyl radicalcontains no further substituents or is substituted as defined for aphenyl radical Z₁ under formula (9); cyclohexyl which is unsubstitutedor substituted by C₁-C₄alkyl, phenylsulfonylamino orC₁-C₄alkylphenylsulfonylamino; 1,2,3,4-tetrahydronaphthyl; or a radicalof the formula

in which

W is a bridge member of the formula —O—, —NH—CO—, —OSO₂—, —NH—SO₂—,—CH₂—NH—SO₂— or —CH₂—N(CH₃)—SO₂—,

R₁₇ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or halogen and

R₁₈ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, halogen oracryloylaminomethyl,

Y₁ is hydrogen; C₁-C₄alkyl; phenyl which is unsubstituted or substitutedby C₁-C₄alkyl, C₁-C₄alkoxy or halogen; phenyl-C₁-C₈alkyl which isunsubstituted or substituted in the phenyl ring by C₁-C₄alkyl,C₁-C₄alkoxy, halogen or benzoylaminomethyl; cyclohexyl which isunsubstituted or substituted by C₁-C₄alkyl; or1,2,3,4-tetrahydronaphthyl, or anthraquinone dyes of the formula

in which Z₂ is phenyl which is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy or halogen or cyclohexyl which is unsubstitutedor substituted by C₁-C₄alkyl or benzyl and Y₂ is C₁-C₄alkyl or is asdefined above for Z₂, or anthraquinone dyes of the formula

in which R₁₉ and R₂₀ are hydrogen or methyl.

Particularly preferred anthraquinone dyes of the formula (2) areanthraquinone dyes of the formula

1:2 chromium or 1:2 cobalt complex azo dyes are, in particular, 1:2cobalt complex dyes of two identical or different azo compounds from thegroup comprising compounds of the formulae (3), (4) and (5), and 1:2chromium complex dyes of two identical or different azo compounds fromthe group comprising compounds of the formulae (5) and (6).

Particularly preferred 1:2 chromium or 1:2 cobalt complex azo dyes aredyes of the formula

Especially preferred dye mixtures are those which comprise, in additionto the 1:2 cobalt complex formazan dye, at least one dye of the formulae(9), (10), (11) and (43) to (50), in particular at least one dye of theformulae (12) to (50). The dye of the formula (50) is especiallypreferred here. The 1:2 cobalt complex formazan dye here is as definedand preferred above.

The anthraquinone dyes of the formula (2) and the 1:2 chromium and 1:2cobalt complex azo dyes are known or can be obtained analogously toknown compounds. Thus, anthraquinone dyes of the formula (2) can beobtained, for example, analogously to processes defined in GB-A-903 590,GB-A-945 806, GB-A-2 009 214 and U.S. Pat. No. 3,491,125. The 1:2chromium and 1:2 cobalt complex azo dyes can be obtained, for example,analogously to processes defined in GB-A-716 753, GB-A-719 274, GB-A-745641 and GB-A-851 861.

Some of the 1:2 cobalt complex formazan dyes of the formula (1) arenovel. The 1:2 cobalt complex formazan dyes of the formula (1) can beobtained analogously to the process defined for the preparation of thenovel 1:2 cobalt complex formazan dyes.

The dye mixture according to the invention can be prepared, for example,by mixing the individual dyes. This mixing process is carried out, forexample, in suitable mills, for example bead and pinned disc mills, andin kneaders or mixers.

The dye mixtures furthermore can be prepared, for example, by spraydrying the aqueous dye mixtures.

The dye mixtures preferably comprise 5 to 95% by weight, in particular10 to 90% by weight and preferably 20 to 80% by weight, of the 1:2cobalt complex formazan dye, based on the total amount of the dyes ofthe mixtures.

If they contain sulfo groups, the individual dyes are present in the dyemixtures according to the invention either in the form of their freesulfonic acid or, preferably, as salts thereof, for example alkalimetal, alkaline earth metal or ammonium salts or as salts of an organicamine. Examples are the sodium, lithium or ammonium salts or the salt oftriethanolamine. Counter-ions of metal complex dyes having a negativecharge are, for example, the cations of the abovementioned salts.

The dye mixtures as a rule contain further additives, for example sodiumchloride or dextrin.

The invention furthermore relates to a process for dyeing or printingfibre materials containing hydroxyl groups or containing nitrogen usingthe dye mixtures according to the invention.

Fibre materials are preferably both natural polyamide fibre materials,for example silk or, in particular, wool, and synthetic polyamide fibrematerials, for example polyamide 6 or polyamide 6.6, or wool- orpolyamide-containing blend fabrics. Synthetic polyamide fibre materialsare of particular interest here.

The fibre material mentioned can be in widely varying processing forms,for example as fibres, yarn, woven fabric or knitted fabric, and inparticular in the form of carpets.

The dyeing or printing can be carried out in customary dyeing orprinting apparatuses. The dye liquors or printing pastes can comprisefurther additives, for example wetting agents, antifoams, levellingagents or agents which influence the property of the textile material,for example softening agents, additives for flameproofing or soil-,water- and oil-repellent agents, as well as water-softening agents andnatural or synthetic thickeners, for example alginates and celluloseethers.

The dye mixtures according to the invention give level dyeings havinggood all-round properties, in particular good fastness to rubbing, wetprocessing, wet rubbing, light and hot light. The dye mixtures accordingto the invention furthermore have a good water-solubility and resistanceto hard water and are distinguished by good affinity properties and goodcombinability with other dyes.

The invention furthermore relates to symmetric 1:2 cobalt complexformazan dyes of compounds of the formula

in which

R₂₁ is hydrogen, halogen or C₁-C₄alkylsulfonyl which is unsubstituted orhydroxyl-substituted and

a) A₁ is a radical of the formula

B₁ is a radical of the formula

in which

R₂₂ is hydrogen or unsubstituted or hydroxyl-substituted C₁-C₄alkyl,

R₂₂′ is hydrogen or C₁-C₄alkyl,

R₂₃ and R₂₃′ independently of one another are each hydrogen, C₁-C₄alkylor halogen,

R₂₄ is C₁-C₄alkanoylamino or N—C₁-C₄alkylsulfamoyl which isunsubstituted or substituted in the alkyl moiety by hydroxyl,

R₂₅ is hydrogen or halogen and

R₂₆ is hydrogen, unsubstituted or hydroxyl-substituted C₁-C₄alkyl orphenyl which is unsubstituted or substituted by sulfo, carboxyl orsulfamoyl, or

b) A₁ is a radical of the formula

B₁ is a radical of the formula

in which

R₂₇ is hydrogen or halogen,

R₂₈ is hydrogen or sulfamoyl and

R₂₅ and R₂₆ independently are as defined above.

C₁-C₄alkyl here is generally methyl, ethyl, n- or iso-propyl or n, iso-,sec- or tert-butyl, and preferably methyl or ethyl. Examples ofunsubstituted or hydroxyl-substituted C₁-C₄alkyl are, in particular,methyl, ethyl or 2-hydroxyethyl. Halogen is generally, for example,fluorine, bromine or, in particular, chlorine. Examples of unsubstitutedor hydroxyl-substituted C₁-C₄alkylsulfonyl are methylsulfonyl,ethylsulfonyl or 2-hydroxyethylsulfonyl. Examples of C₁-C₄alkanoylaminoare acetylamino or propionylamino.

Preferred embodiments of the present invention relate to:

a) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula

in which R₂₁ is hydrogen, chlorine or fluorine, R₂₂ is hydrogen, methyl,ethyl or 2-hydroxyethyl,R₂₅ is hydrogen or chlorine and R₂₆ is hydrogen,methyl, ethyl, 2-hydroxyethyl, phenyl, 2- or 3-carboxyphenyl, 2- or3-sulfamoylphenyl or 2- or 3-sulfophenyl.

b) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula (51a) defined above, in which R₂₁ is hydrogen, chlorine orfluorine, R₂₂ is hydrogen, methyl or ethyl, R₂₅ is chlorine and R₂₆ ishydrogen, methyl, ethyl, 2-carboxyphenyl, 2-sulfamoylphenyl or2-sulfophenyl.

c) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula

in which R₂₁ is hydrogen or chlorine, R₂₂′ is hydrogen, methyl or ethyl,R₂₄′ is N-methylsulfamoyl, N-ethylsulfamoyl orN-2-hydroxyethylsulfamoyl, R₂₅ is hydrogen or chlorine and R₂₆ ishydrogen, methyl or ethyl.

d) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula (51b) defined above, in which R₂₁ is hydrogen, R₂₂′ is hydrogen,R₂₄ is acetylamino or, in particular, propionylamino, R₂₅ is hydrogen orchlorine and R₂₆ is hydrogen, methyl or ethyl.

e) symmetric 1:2 cobalt complex formazan dyes of compounds of theformula

in which R₂₁ is hydrogen, methylsulfonyl, ethylsulfonyl or2-hydroxyethylsulfonyl, R₂₅ is hydrogen or chlorine, R₂₆ is hydrogen,methyl, ethyl, 2-sulfophenyl, 2-carboxyphenyl or 2-sulfamoylphenyl, R₂₇is hydrogen or chlorine and R₂₈ is hydrogen or sulfamoyl.

f) Symmetric 1:2 cobalt complex formazan dyes of the formula

in which M^(⊕) is a cation. A cation M^(⊕) is, for example, a proton or,preferably, a metal cation, for example an alkali metal cation, such asNa^(⊕), K^(⊕) or Li^(⊕) furthermore can be an ammonium cation or theammonium salt of an organic amine, for example the salt of mono-, di- ortriethanolamine.

The compounds of the formula (51) can be prepared in a manner which isknown per se, for example by diazotizing a compound of the formula

B₁—NH₂  (57),

coupling the product to the hydrazone of the formula

and metallizing the resulting metal-free compound with a cobalt salt, inwhich the variables R₂₁, A₁ and B₁ are as defined under formula (51).

The diazotization of the amine of the formula (57) is as a rule carriedout by the action of nitrous acid in aqueous-mineral acid solution at alow temperature, and the coupling to the coupling component of theformula (58) is advantageously carried out at alkaline pH values, forexample at pH≧9 and in particular at a pH of 10 to 12.

The metallization takes place, for example, in an aqueous medium whichhas an alkaline pH, for example a value of 7.5 to 12, and preferably 8to 12, at a temperature of 40 to 100° C., and in particular at 40 to 60°C. Suitable cobalt salts are, for example, the acetate, nitrate,chloride or, in particular, the sulfate.

The coupling of the diazotized compound of the formula (57) to thecompound of the formula (58) and the metallization can be carried out insuccession or also simultaneously, for example by adding the diazosuspension together with the cobalt salt to the solution of thehydrazone.

The compounds of the formulae (57) and (58) are known per se or can beprepared analogously to known compounds.

The dyes according to the invention as a rule contain further additives,for example sodium chloride or dextrin.

The invention furthermore relates to a process for dyeing or printingfibre materials containing hydroxyl groups or containing nitrogen withthe dyes according to the invention.

Preferred fibre materials are both natural polyamide fibre materials,for example silk or, in particular, wool, and synthetic polyamide fibrematerials, for example polyamide 6 or polyamide 6.6, or wool- orpolyamide-containing blend fabrics. Synthetic polyamide fibre materialsare of particular interest here.

The fibre material mentioned can be in widely varying processing forms,for example as fibres, yarn, woven fabric or knitted fabric, and inparticular in the form of carpets.

The dyeing or printing can be carried out in customary dyeing orprinting apparatuses. The dye liquors or printing pastes can comprisefurther additives, for example wetting agents, antifoams, levellingagents or agents which influence the property of the textile material,for example softening agents, additives for flameproofing or soil-,water- and oil-repellent agents, as well as water-softening agents andnatural or synthetic thickeners, for example alginates and celluloseethers.

The dyes according to the invention give level dyeings having goodall-round properties, in particular good fastness to rubbing, wetprocessing, wet rubbing, light and hot light. The dyes according to theinvention furthermore have a good water-solubility and resistance tohard water and are distinguished by good affinity properties and by goodcombinability with other dyes.

In the following examples, parts are by weight. The temperatures aredegrees Celsius. Parts by weight bear the same relation to parts byvolume as the gram to the cubic centimeter.

EXAMPLE 1A

For preparation of a dye mixture which comprises the dyes of theformulae

55 parts of the dye of the formula (101), 13 parts of the dye of theformula (102), 14 parts of the dye of the formula (103) and 18 parts ofthe dye of the formula (104) are homogeneously mixed in a mixer to give100 parts of the mixture called dye mixture A below.

EXAMPLE 1B

To prepare a dye mixture comprising the dyes of the formulae (101) and(103) and the dye of the formula

22 parts of the dye of the formula (101), 47 parts of the dye of theformula (103) and 31 parts of the dye of the formula (105) arehomogeneously mixed in a mixer to give 100 parts of the mixture calleddye mixture B below.

EXAMPLE 1C

To prepare a dye mixture which comprises the dyes of the formulae (101),(102) and (103), 20 parts of the dye of the formula (101), 35 parts ofthe dye of the formula (102) and 45 parts of the dye of the formula(103) are homogeneously mixed in a mixer to give 100 parts of themixture called dye mixture C below.

EXAMPLE 1D

To prepare a dye mixture which comprises the dyes of the formulae (101)and (105) and the dye of the formula

22 parts of the dye of the formula (101), 32 parts of the dye of theformula (105) and 46 parts of the dye of the formula (106) arehomogeneously mixed in a mixer to give 100 parts of the mixture calleddye mixture D below.

EXAMPLE 1E

To prepare a dye mixture which comprises the dyes of the formulae (101),(102) and (106), 21 parts of the dye of the formula (101), 36 parts ofthe dye of the formula (102) and 43 parts of the dye of the formula(106) are homogeneously mixed in a mixer to give 100 parts of themixture called dye mixture E below.

EXAMPLE 1F

To prepare a dye mixture which comprises the dyes of the formulae (101)and (106) and the dyes of the formulae

40 parts of the dye of the formula (101), 7 parts of the dye of theformula (106), 40 parts of the dye of the formula (107) and 13 parts ofthe dye of the formula (108) are homogeneously mixed in a mixer to give100 pails of the mixture called dye mixture F below.

EXAMPLE 1G

To prepare a dye mixture which comprises the dyes of the formulae (101),(106) and (107), 41 parts of the dye of the formula (101), 4 parts ofthe dye of the formula (106) and 55 parts of the dye of the formula(107) are homogeneously mixed in a mixer to give 100 parts of themixture called dye mixture G below.

EXAMPLE 1H

To prepare a dye mixture which comprises the dye of the formula (101)and the dye of the formula

45 parts of the dye of the formula (101) and 55 parts of the dye of theformula (109) are homogeneously mixed in a mixer to give 100 parts ofthe mixture called dye mixture H below.

EXAMPLE 1I

To prepare a dye mixture which comprises the dye of the formula (101)and the dye of the formula

45 parts of the dye of the formula (101) and 55 parts of the dye of theformula (110) are homogeneously mixed in a mixer to give 100 parts ofthe mixture called dye mixture I below.

EXAMPLE 1J

To prepare a dye mixture which comprises the dye of the formula (101),the dye of the formula

22 parts of the dye of the formula (101), 31 parts of the dye of theformula (111) and 47 parts of the dye of the formula (112) arehomogeneously mixed in a mixer to give 100 parts of the mixture calleddye mixture J below.

EXAMPLE 1K

To prepare a dye mixture which comprises the dye of the formula

30 parts of the dye of the formula (113) and 70 parts of the dye of theformula (114) are homogeneously mixed in a mixer to give 100 parts ofthe mixture called dye mixture K below.

EXAMPLE 1L

To prepare a dye mixture which comprises the dye of the formula (101)and the dye of the formula

50 parts of the dye of the formula (101) and 50 parts of the dye of theformula (115) are homogeneously mixed in a mixer to give 100 parts ofthe mixture called dye mixture L below.

EXAMPLE 2

86.1 g of 4-sulfamoylaniline are introduced into 200 ml of water, the pHis brought to about 11.5 with sodium hydroxide solution and the mixtureis heated at about 50° C. until a solution has formed. 125 ml of 4Nsodium nitrite solution are allowed to run rapidly into this solution.After the temperature has dropped to about 35 to 40° C., the resultingsolution is allowed to run into a cold mixture, at −5 to 0° C., of 100 gof ice and 400 ml of 31% naphthalene-1-sulfonic acid solution. Themixture is kept at 0 to 2° C. for about 1 hour, a little more nitritesolution is added if appropriate, and at the end the excess nitrite isdestroyed with sulfamic acid.

The pH of the solution obtained above is brought to 4.5 to 5 with sodiumhydroxide solution, and a suspension of 104.6 g of sodium pyrosulfite in100 ml of water is then added dropwise at 0 to 5° C. in the course ofabout 30 to 45 minutes; during this addition, the pH is kept at 6 to 6.5by addition of sodium hydroxide solution. The mixture is subsequentlystirred at about 5° C. for 1 hour, at 40 to 50° C. for a further 2 hoursand finally at room temperature overnight. After addition of HCl (pH<1), the SO₂ formed is driven off with compressed air. Thehydrazine-containing mixture is heated to 60 to 70° C. and 50 ml ofbenzaldehyde are added dropwise in the course of about 15 minutes. Themixture is subsequently stirred at 65 to 70° C. for about 2 to 2.5 hoursand cooled to room temperature, and the compound which has crystallizedout, of the formula

is filtered off. After washing with water and hydrochloric acid, theproduct is dried in vacuo.

EXAMPLE 3

30.3 g of 2-amino-4-N-methylsulfamoylphenol are dissolved in 180 ml ofwater, the pH is rendered acid with HCl and the temperature is cooled to0 to 5° C. 37.5 ml of 4N sodium nitrite solution are added at thistemperature and the amino compound is diazotized.

After the excess nitrite has been destroyed with sulfamic acid and thepH has been increased to 3 with sodium hydroxide solution, the diazosuspension is added in small portions, in the course of about 1.5 hours,to a solution, which has been brought to pH 12.3 to 12.5 with sodiumhydroxide solution, of 41.3 g of the hydrazone obtained according toExample 2 in about 350 ml of water at 40 to 45° C. and the pH is kept at12.3 to 12.5 by addition of sodium hydroxide solution. The mixture issubsequently stirred at 40 to 45° C. for about 30 minutes, the pH islowered to about 9.5 with hydrochloric acid and the metal-free dye ofthe formula

is filtered off, after cooling, and washed with sodium chloridesolution.

EXAMPLE 4

The crude dye obtained according to Example 3 is homogeneously suspendedin 600 ml of water and the suspension is heated to about 60 to 70° C.The pH is brought to about 8.5 to 9.5 with sodium carbonate solution,and 70 ml of 1 molar CoSO_(4/)tartaric acid solution are added dropwiseat 60 to 65° C. in the course of about 30 minutes, while stirring, thepH being kept between 8.5 and 9 by addition of further sodium carbonatesolution. The colour shade changes from red to blue and the 1:2 Cocomplex crystallizes out. The pH is brought to 11 to 11.5 with sodiumhydroxide solution, stirring is continued for about 30 minutes, the pHis lowered to about 9.5 with hydrochloric acid, the compound of theformula

is filtered off and the precipitate is washed with sodium chloridesolution. Examples 5 to 34: The symmetric 1:2 cobalt complexes ofcompounds of the general formula

in which the variables are as defined in the table, can be preparedanalogously to those in Examples 2 to 4:

Example No. A B C D E  5 SO₂NH₂ H H SO₂NHCH₃ H  6 SO₂NH₂ H H H SO₂NH₂  7SO₂NH₂ H H SO₂NH₂ H  8 SO₂NH₂ H H SO₂NHCH₃ Cl  9 SO₂NH₂ H H SO₂NH₂ Cl 10SO₂NH₂ H H

H 11 SO₂NH₂ H Cl H

12 SO₂NHCH₃ H H H SO₂NH₂ 13 SO₂NH₂ H Cl SO₂NH₂ Cl 14 SO₂NH₂ H ClSO₂NHCH₃ Cl 15 SO₂NH₂ H F SO₂NH₂ Cl 16 SO₂NH₂ H F SO₂NHCH₃ Cl 17 HSO₂NH₂ H SO₂NH₂ Cl 18 H SO₂NH₂ H SO₂NHCH₃ Cl 19 H SO₂NH₂ H H

20 CH₃ SO₂NHC₂H₅OH H SO₂NH₂ Cl 21 CH₃ SO₂NHC₂H₅OH H SO₂NHCH₃ Cl 22 CH₃SO₂NHC₂H₅OH Cl SO₂NHCH₃ Cl 23 CH₃ SO₂NHC₂H₅OH Cl SO₂NH₂ Cl 24 H NHCOC₂H₅H H SO₂NH₂ 25 H NHCOC₂H₅ H H SO₂NHCH₃ 26 H NHCOC₂H₅ H SO₂NH₂ Cl 27 HNHCOC₂H₅ H SO₂NHCH₃ Cl 28 Cl H H SO₂NH₂ H 29 Cl H H SO₂NH₂ Cl 30 Cl H HSO₂NHCH₃ Cl 31 Cl H H

H 32 SO₂NH₂ H H H

33 H H SO₂C₂H₅OH SO₂NHCH₃ Cl 34 H SO₂NH₂ H

H

EXAMPLES 35 TO 38

The symmetric 1:2 cobalt complexes of the compounds of the generalformula

in which the variables C and D are as defined in the table, can beprepared analogously to those in Examples 2 to 4:

Example No. C D 35 H SO₂NH₂ 36 H SO₂NHCH₃ 37 Cl SO₂NH₂ 38 Cl SO₂NHCH₃

EXAMPLES 39 TO 42

The symmetric 1:2 cobalt complexes of the compounds of the generalformula

in which the variables C and D are as defined in the table, can beprepared analogously to those in Examples 2 to 4:

Example No. C D 39 H SO₂NH₂ 40 H SO₂NHCH₃ 41 Cl SO₂NH₂ 42 Cl SO₂NHCH₃

Dyeing Example 1

10 parts of polyamide 6.6 woven fabric are dyed in 200 parts of anaqueous liquor which comprises 0.27%, based on the fibre weight, of dyemixture A according to Example 1A and is brought to pH 6 with aceticacid and sodium acetate. The dyebath is heated to 98° C. in the courseof 45 minutes, kept at 96° C. to 98° C. for 60 minutes and then cooledto 70° C. in the course of 15 minutes. The dyed woven fabric is thenremoved and rinsed and dried in the customary manner. A woven fabricdyed in a grey colour shade is obtained.

Dyeing Examples 2 to 7

The procedure described in Dyeing Example 1 is repeated, except that thedye mixtures defined in column 2 in the following Table 1 are used inplace of dye mixture A, affording polyamide 6.6 woven fabrics dyed inthe colour shades defined in column 3.

TABLE 1 Ex- ample Dye mixture Colour shade on polyamide 2 1.06% of dyemixture B brown 3 1.13% of dye mixture C brown 4 1.03% of dye mixture Dbrown 5 1.10% of dye mixture E brown 6 1.06% of dye mixture J brown 71.06% of dye mixture L brown

The procedure described in Dyeing Examples 1 to 7 is repeated, exceptthat in each case corresponding dye mixtures which comprise the dye ofthe formula

in the same amount by weight in place of the dye of the formula (101)are used, affording polyamide 6.6 woven fabrics dyed in the colourshades defined in the particular examples.

Dyeing Example 8

10 parts of polyamide 6.6 woven fabric are dyed in 200 parts of anaqueous liquor which comprises 1.5%, based on the fibre weight, of dyemixture F according to Example 1F and is brought to pH 6 with phosphatebuffer (NaH₂PO₄/Na₂HPO₄). The dyebath is heated to 98° C. in the courseof 45 minutes and left at this temperature for 60 minutes. The dyedwoven fabric is then removed and rinsed and dyed in the customarymanner. A woven fabric dyed in a blue colour shade is obtained.

Dyeing Examples 9 to 12

The procedure in Dyeing Example 8 is repeated, except that the dyemixtures defined in column 2 in the following Table 2 are used in placeof dye mixture F, affording polyamide 6.6 woven fabrics dyed in thecolour shades defined in column 3.

TABLE 2 Ex- ample Dye mixture Colour shade on polyamide 9 1.75% of dyemixture G blue 10 1.5% of dye mixture H blue 11 1.5% of dye mixture Iblue 12 1.5% of dye mixture K blue

The procedure described in Dyeing Examples 8 to 12 is repeated, exceptthat in each case corresponding dye mixtures which comprise the dye ofthe formula (117) in the same amount by weight in place of the dye ofthe formula (101) are used, affording polyamide 6.6 woven fabrics dyedin the colour shades defined in the particular examples.

Dyeing Example 13

10 parts of polyamide 6.6 fibre material (Helanca tricot) are dyed in500 parts of an aqueous liquor which comprises 2 g/l of ammonium acetateand 0.5%, based on the fibre weight, of the blue dye of the formula(118) according to Example 4 and is brought to pH 5 with acetic acid.

The dyeing time at a temperature of 98° C. is 30 to 90 minutes. The dyedpolyamide fibre material is then removed and rinsed and dried in thecustomary manner. A piece of woven fabric which is dyed completelylevelly in a blue colour shade and shows no material-related stripinessat all is obtained.

Dyeing Example 14

10 parts of polyamide 6.6 yarn are dyed in 400 parts of an aqueousliquor which comprises 1.5 g/l of ammonium acetate and 0.5%, based onthe fibre weight, of the dye of the formula (118) according to Example 4and is brought to pH 5.5 with acetic acid. The dyebath is heated to 98°C. in the course of 30 minutes and kept at 96° C. to 98° C. for 60minutes. The dyed yarn is then removed and rinsed and dried in thecustomary manner. A yarn dyed in a blue colour shade is obtained.

What is claimed is:
 1. A dye mixture wherein the dyes consistessentially of 5 to 95% by weight of the 1:2 cobalt complex dye of theformazan compound of the formula

together with at least one anthraquinone dye of the formulae (2) and(11)

in which Z is phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, hydroxyl, nitro, carboxyl,cyano, amino, halogen, benzoylaminomethyl, chloroacetylamino,chloroacetylaminomethyl, α-chloroacryloylaminomethyl,acryloylaminomethyl, or by phenoxy, phenylcarbonylamino,phenylsulfonyloxy, phenylsulfonylamino, phenylsulfonylaminomethyl orN-methyl-phenylsulfonylaminomethyl, where the phenyl radicals contain nofurther substituents or are further substituted by C₁-C₁₂alkyl,C₁-C₄alkoxy, C₂-C₄alkanoylamino, hydroxyl, nitro, carboxyl, cyano,amino, halogen, benzoylaminomethyl, chloroacetylamino,chloroacetylaminomethyl, α-chloroacryloylaminomethyl oracryloylaminomethyl, or Z is C₁-C₈alkyl which is unsubstituted or issubstituted by phenyl, where the phenyl radical contains no furthersubstituents or is further substituted as defined for a phenyl radical Zabove, or Z is cyclohexyl which is unsubstituted or is substituted byC₁-C₁₂alkyl or phenylsulfonylamino or benzyl, where the phenyl radicalscontain no further substituents or are further substituted byC₁-C₁₂alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino or halogen, or Z is1,2,3,4-tetrahydronaphthyl, Y is hydrogen or is as defined for Z above,and in which anthraquinone dye of the formula (2) the ring V contains nofurther substituents or is further substituted by one or two hydroxylgroups, and R₁₉ and R₂₀ are hydrogen or methyl, or together with atleast one 1:2 chromium or 1:2 cobalt complex dye of two identical ordifferent azo compounds selected from the group consisting of compoundsof the formulae (3), (4), (5) and (6)

in which R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ andR₁₆ independently of one another are hydrogen, C₁-C₁₂alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, halogen, sulfo, hydroxyl, nitro, sulfamoyl orN—C₁-C₁₂alkylsulfamoyl, which is unsubstituted or further substituted inthe alkyl moiety by hydroxyl or C₁-C₁₂alkoxy.
 2. A dye mixture accordingto claim 1, which comprises, as the anthraquinone dye of the formula(2), an anthraquinone dye of the formula

in which Z₁ is phenyl which is unsubstituted or substituted byC₁-C₁₂alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen,benzoylaminomethyl, chloroacetylamino, chloroacetylaminomethyl orα-chloroacryloylaminomethyl; phenyl-C₁-C₈alkyl, where the phenyl radicalcontains no further substituents or is substituted as defined for aphenyl radical Z₁ above; cyclohexyl which is unsubstituted orsubstituted by C₁-C₄alkyl, phenylsulfonylamino orC₁-C₄alkylphenylsulfonylamino; 1,2,3,4-tetrahydronaphthyl; or a radicalof the formula

in which W is a bridge member of the formula —O—, —NH—CO—, —OSO₂—,—NH—SO₂—, —CH₂—NH—SO₂— or —CH₂—N(CH₃)—SO₂—, R₁₇ is hydrogen, C₁-C₄alkyl,C₁-C₄alkoxy or halogen and R₁₈ is hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy,halogen or acryloylaminomethyl, Y₁ is hydrogen; C₁-C₄alkyl; phenyl whichis unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen;phenyl-C₁-C₈alkyl which is unsubstituted or substituted in the phenylring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or benzoylaminomethyl;cyclohexyl which is unsubstituted or substituted by C₁-C₄alkyl; or1,2,3,4-tetrahydronaphthyl, or an anthraquinone dye of the formula

in which Z₂ is phenyl which is unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy or halogen or cyclohexyl which is unsubstitutedor substituted by C₁-C₄alkyl or benzyl and Y₂ is C₁-C₄alkyl or is asdefined above for Z₂.
 3. A dye mixture according to claim 1, whichcomprises, as the anthraquinone dye of the formula (2) or (11), ananthraquinone dye of the formula


4. A dye mixture according to claim 1, which comprises, as the 1:2chromium or 1:2 cobalt complex azo dye, a dye of the formula